GB2154589A - Improved process for preparing n,n-diacetic acid aminomethylenephosphonic acid - Google Patents
Improved process for preparing n,n-diacetic acid aminomethylenephosphonic acid Download PDFInfo
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- GB2154589A GB2154589A GB08504958A GB8504958A GB2154589A GB 2154589 A GB2154589 A GB 2154589A GB 08504958 A GB08504958 A GB 08504958A GB 8504958 A GB8504958 A GB 8504958A GB 2154589 A GB2154589 A GB 2154589A
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- Prior art keywords
- acid
- alkali metal
- metal salt
- salt
- iminodiacetic
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- 239000002253 acid Substances 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 59
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims description 31
- -1 alkali metal salt Chemical class 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 19
- 239000011707 mineral Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims 3
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims 3
- KKHJQZVEUKJURX-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid;hydrochloride Chemical compound Cl.OC(=O)CNCC(O)=O KKHJQZVEUKJURX-UHFFFAOYSA-N 0.000 claims 2
- 239000012431 aqueous reaction media Substances 0.000 claims 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
1
SPECIFICATION
Improved process for preparing N,N-diacetic acid aminomethylenephosphonic acid GB 2 154 589 A 1 Background of the invention
The present invention relates to an improved process for preparing N,Ndiacetic acid aminomethylenephosphonic acid also known chemically as Nphosphonomethyliminodiacetic acid of the formula (/):
0 0 HO__11 OH I-10 --- P N OH 0 (I) The above compound (1) is an intermediate in the preparation of N- phosphonomethylglycine (glyphosate), an important broad spectrum herbicide. More particularly, the present invention relates to an improved chemical route to (/) in which iminodiacetonitrile (IDAN) is the starting material. IDAN has previously been converted to iminodiacetic acid (IDA) by various process steps beginning with hydrolysis of IDAN with an alkali metal hydroxide, usually sodium hydroxide. This process is described in U.S. Patent 3,904,668.
The practice heretofore in the preparation of IDA for utilization in a phosphonomethylation process to produce N,N-diacetic acid aminomethylenephosphonic acid was to recover IDA from the crude hydrolysate of IDAN by (1) acidification with a mineral acid (typically sulfuric or hydrochloric acid), (2) crystallization of IDA, (3) filtration to recoverthe crystallized IDA, and (4) drying the IDAfor packaging, shipping, etc. A similar recovery of IDA is taught in British Patent 1,575,469. Also, the sodium salt solution separated from IDA in (3) 25 above contained unrecovered IDA which was recovered by evaporating water from the solution resulting in precipitation of sodium salt while leaving the IDA in solution. The precipitated sodium salt was then separated from the residue by filtration and the filtrate recycled to Step (1) above. The above-described process is energy intensive and requires a large investment for the acquisition and maintenance of equipment to recover and purify IDA.
In the past, the recovered IDA from (4) above was utilized in a phosphonomethylation process such as that disclosed in U.S. Patent 3,288,846 to Irani et al, particularly Example IV. In such process the hydrochloride salt is initially formed which is then phosphonomethylated with phosphorous acid (H3PO3) and formaldehyde (CH20). In an alternate method the hydrogen chloride employed to form the hydrochloride salt of IDA and the phosphorous acid employed in phosphonomethylation are provided by the addition of phosphorus trichloride to water. In water, phosphorus trichloride is hydrolyzed to form hydrogen chloride and phosphorous acid. After phosphonomethylation the desired N,N-diacetic acid aminomethylenephos phonic acid is recovered from the reaction mixture by crystallization and filtration. Under current practice there is sufficient unreacted material in the filtrate to require recycle ofthe filtrate. A large amount of hydrogen chloride is released during the hydrolysis of phosphorus trichloride, if employed, and is recovered. 40 Although the above-described procedures are commercially feasible, the need for a reduction in the amount of energy consumed and equipment required makes further improvement highly desirable.
Summary of the invention
In accordance with the present invention there is provided an improved process for preparing N,N-diacetic 45 acid aminomethylenephosphonic acid (1) wherein IDAN is hydrolyzed with an alkali metal base to form an alkali metal salt of IDA which is converted to IDA strong acid salt and phosphonomethylated. The improvement comprises reacting in series the alkali metal salt of IDA with a strong mineral acid to form the strong acid salt of IDA and the alkali metal salt of the strong acid and then phosphonomethylating by reacting the strong acid salt of IDA with phosphorous acid and formaldehyde to provide (1) with an alkali metal salt. Then an amount of water is added to the reaction mixture suff icient to dissolve the alkali metal salt and (1) is separated as a precipitate.
Further within the scope of this invention, it has been discovered that the hydrolysate of [DAN containing the alkali metal salt of IDA can be employed directly in the above- described improved process resulting in the production of (1) in high yield and purity. Surprisingly, it has been found that there is no need to isolate 55 the alkali metal salt of IDA from the crude hydrolysate.
Because of the elimination of numerous steps for the conversion, purification, and recovery of IDA from the crude hydrolysate of [DAN, the process of this invention offers a more economical route to (1) than previously known.
Detailed description of the invention
According to the process of this invention, N,N-diacetic acid aminomethylenephosphonic acid can be prepared from the alkali salt of iminodiacetic acid, preferably Na21DA, by first converting the alkali metal salt to the strong acid salt of IDA and the alkali metal salt of the strong acid.
2 GB 2 154 589 A 2 As employed herein the term "strong mineral acid" includes those mineral acids having a pKa lower than phosphorous acid employed in the phosphonomethylation step. Typical such acids include sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid and the like. Hydrochloric acid is preferred because it is most economical when provided by conversion of phosphorus trichloride in situ as further explained below.
Sulfuric acid is preferred when phosphorous acid is employed directly. Because hydrochloric acid is preferred, the invention will be further described with reference to hydrochloric acid although any other suitable strong mineral acid can be employed in its place.
Although the process of this invention is described with Na21DA as a starting material, other IDA alkali salts, such as K21DA, may also be used.
In a preferred embodiment phosphorus trichloride is hydrolyzed to phosphorous acid while the Na21DA is 10 simultaneously transformed to iminodiacetic. acid hydrochloride (IDA.HCI) and sodium chloride according to the following general equations:
PC13 + 3H20 H3P03 + 3HCI 15 Na21DA + 2HCI IDA + 2NaCI IDA+ HCI, IDA-HCI The reaction is best carried out at reflux temperatures of about 110'-1 20'C. Lower temperatures can be used, but this tends to reduce the evolution of HCI and the reaction mixture would tend to thicken and make agitation difficult. Alternatively HCI and phosphorous acid can be combined with Na21DA to form IDA-HCI 25 and sodium chloride.
In this reaction the phosphorus trichloride is hydrolyzed to phosphorous acid in the Na21DA solution and a slurry is formed. HCI, which results from hydrolysis of phosphorus trichloride, acidifies the Na21DA to its hydrochloride salt and to NaCl, both of which precipitate. Optionally, additional HCI can be added to ensure complete formation of the IDA hydrochloride salt. The amount of additional HC1 which can be added can be 30 determined by procedures well known in the art.
The concentration of the Na21DA solution is an important variable in the process. Preferably, concentration should be in the range of 38-441/6 Na2lDA by weight. Higher concentrations can be used, but these may be undesirable because the slurry formed in the PC13 hydrolysis step will tend to thicken and be hard to agitate. Lower concentrations (<38% Na21DA) can be used, but this tends to reduce yield because more IDA will be 35 left unreacted in the phosphonomethylation step.
The IDA-HCI in the reaction mixture is then phosphonomethylated by adding formaldehyde (CH20) thereto. For convenience, formalin, a 44% by weight CH20 solution stabilized with 1 % MeOH, can be used in this step, although all sources of formaldehyde would be satisfactory for practicing this invention, eg., paraformaldehyde. The reaction proceeds according to the following equation:
H3P03 + CH20 + IDA.HCI (H02)P(O)CH2N(CH2COOH)2 + H20 + HCL Ordinarily, phosphonomethylation is conducted at reflux temperatures ranging from 108'-120'C.
To ensure high conversion of IDA during phosphonomethylation, formaldehyde and phosphorous acid should be in stoichiometric excess. Generally, the mole ratio of phosphorus trichloride to alkali metal iminodiacetic acid is in the range of from about 0.8 to about 1.4. A 1.1 mole ratio Of PC13 to IDA and a 1.2 mole ratio of formaldehyde to IDA are preferred.
Under certain conditions IDA and CH20 can reactto form N-methyl iminodiacetic acid (N-Me IDA) an 50 undesired by-product.
0 1 /1-OH CHa -N N-Methyl IDA \ OH 55 0 This type of side reaction can be minimized with sufficient strong mineral acid, preferably HCI, in the reaction mixture. In the preferred process with HCI as the only strong mineral acid present, the concentration 60 of HCI in excess of the hydrochloride salt of IDA in the reaction mass should be at least 5% by weight (calculated on the basis of HCI and H20, only), although it may range from 0% to 20%.
3 GB 2 154 589 A 3 In the preferred embodiment of this invention it is preferable to add a portion of the total Na21DA charge along with the CH20 during the phosphonomethylation step. The Na21DA will be acidified by the liberated HCI according to the reaction shown below.
IDA.HCI + CH20 + H3P03) (1) + HCI + H20 5 By adding Na21DA during the phosphonomethylation step it is possible to minimize the amount of acid necessary in the phosphonomethylation step without substantially increasing by-product N-Me IDA. The Na21DA can be added without noticeable increased formation of N-Me IDA as long as the concentration of HCI in excess of the hydrochloride salt of IDA is at or above at least 5% (calculated on the basis of HCI and 10 H20, only). Addition of Na21DA during the phosphonomethylation step has the further advantage of utilizing hydrogen chloride more efficiently. During phosphonomethylation hydrogen chloride is given off and is utilized to convert the additional Na21DA to the hydrochloride salt of IDA. Preferably, 20% to 25% of the total charge of Na21DA can be added during the phosphonomethylation step.
A by-product of this process is sodium salt of a strong mineral acid. In a preferred embodiment following 15 phosphonomethylation, a dilute base, such as sodium hydroxide, is added to the reaction mixture so that the pH of the mixture is adjusted to the isoelectric point of the N,N- diacetic acid aminomethylenephosphonic acid, i.e., the point of minimum solubility. The charge of base is most conveniently determined by calculation. The amount of base is such that approximately all the HCI in the reaction mixture is neutralized.
The concentration of the base is such that sufficient water is present to dissolve all by-product NaCl in the 20 final mixture. The calculations are well known to those skilled in the art.
In the reaction product, N,N-diacetic acid amino methylenephosphonic acid is present as a solid precipitate. It can be separated from the mixture by filtration and then washed and dried. The N,N-diacetic acid aminomethylenephosphonic acid is obtained in high yield at a cost and energy usage significantly below that of known commercial processes which begin with IDAN as a starting material and wherein IDA is 25 isolated from the crude hydrolysate.
The process of this invention is illustrated in the following examples in which concentrations are by weight and temperature is in 'C unless otherwise indicated. A 500 ml round bottom flask complete with condenser, agitator, heating mantle and temperature regulating means was used as the reactor in all examples.
Phosphorus trichloride and formaldehyde were charged via 50 cc syringes and a syringe pump. Filtering was 30 done on an 11 cm diameter porcelain filter with Whatman #3 qualitative filter paper. Pressure was atmospheric.
In the following representative examples the Na21DA solution employed was a crude hydrolysate of [DAN.
The crude hydrolysate was obtained by hydrolyzing IDAN in sodium hydroxide solution using a mole ratio of sodium hydroxide to IDAN of about 2.5. The hydrolysis was performed under vacuum to strip out the by-product NH3. In Example 2, the Na21DA solution composition was adjusted slightly, prior to use, by atmospheric evaporation and addition of a small amount of IDA to increase Na21DA content and reduce NaOH content.
Example 1
184.0 g of Na21DA solution was charged to the reactor. The solution analyzed 37.96% Na21DA and 4.37% NaOH by simple titration. IDA assay by HPLC analysis was 28.25%.17.4 g of 37% HCI was then added. The mixture was heated to boiling, and 11 mi of water was distilled.
With the temperature controlled at 110'-1 12C, 64 g Of PC13 was added at a rate of.764 ml/min. The composition at the end of the PC13 addition was calculated to be: 66.9 g IDA-HCI, 57.93 g NaCl, 6.86 g HCI, 45 84.55 g H20, and 38.17 g H3PO3. The concentration of HCI was 7.5% (HCi and H20 basis).
With the temperature controlled at 108'-11 O'C, 32.0 g of 44% CH20 (as formalin) was added over a period of 1 hour. The mixture was held an additional 90 minutes after the formalin addition was complete.
The mixture was cooled with an ice bath during which 190.80 g of 12.2% NaOH aqueous solution was added. The temperature of the cooled mixture was 15'C.
The mixture was filtered, and a wet cake was recovered which was washed with 46 g H20 and dried. 78.21 g of dry solids were recovered. Product assayed 99.75% N,N-diacetic acid aminomethylenephosphonic acid.
Isolated yield was 87.9% [(78.21 x.9975)/(184.0 x.2825) x 133/227].
Example 2
159.96 g of Na21DA solution were charged to the reactor. The solution was analyzed as in Example 1 and found to contain 41.85% Na21DA and 1.95% NaOH.
The solution was heated to reflux (1 13'C). 73.13 g Of PC13 were added at. 745 ml/min. The mixture was maintained at refluxing conditions throughout the PC13 addition. Near the end of the PC13 addition, 3.5 g of HCI was evolved and collected in a water scrubber. The temperature at the end of the PC13 addition was 60 11 7'C.
With the temperature controlled at 108'-11 O'C, 38.8 g of 44% formalin and 40.23 g of Na21DA solution were added to the batch. The formalin was added uniformly over a period of 68 minutes. The Na21DA solution was added uniformly over 60 minutes. The addition of Na21DA solution was started 3 minutes after the start of formalin addition. The batch was then held an additional 90 minutes after the end of the formalin addition. 65 4 GB 2 154 589 A 4 The batch was allowed to cool to 45'C. During the cool down, 145.75 g of 10.7% NaOH were added. The batch was filtered. The recovered wet cake was washed with 105 ml of water and dried. 97.88 g of 98.4% assay N,N-diacetic acid aminomethylenephosphonic acid was recovered. Isolated yield was 89.6% [(97.88 x 984)/(159.96 + 40.23) x.4185) x 177/2271.
Although the present invention has been described above with respectto several embodiments, the 5 details are not to be construed as limitations except as to the extent indicated in the following claims.
Claims (20)
1. A process for preparing N,N-diacetic acid aminomethylenephosphonic acid which comprises reacting 10 in series, an alkali metal salt of iminodiacetic acid with a strong mineral acid to form the strong mineral acid salt of iminodiacetic acid and the alkali metal salt of the strong mineral acid and phosphonomethylating the salt of iminodiacetic acid by reaction with formaldehyde and phosphorous acid to provide a mixture of N,N-diacetic acid aminomethylenephosphonic acid and an alkali metal salt; after the phosphonomethylation step adding an amount of water to the reaction mixture sufficient to dissolve the alkali metal salt and 15 separating said N,N-diacetic acid aminomethylenephosphonic acid as a precipitate.
2. The process of Claim 1 wherein the strong mineral acid is hydrochloric acid.
3. The process of Claim 2 wherein the alkali metal salt of iminodiacetic acid is the disodiurn salt.
4. The process of Claim 1 wherein the alkali metal salt of iminodiacetic acid is the dipotassium salt.
5. The process of Claim 3 wherein the hydrogen chloride and phosphorous acid is provided by adding 20 phosphorus trichloride to an aqueous reaction medium.
6. The process of Claim 5 wherein the phosphorus trichloride and the total amount of disodiurn salt of iminodiacetic acid are present in the reaction mixture in the mole ratio of about 0.8 to 1.4.
7. The process of Claim 1 wherein the water added after the phosphonomethylation step contains an amount of base so as to neutralize excess strong mineral acid in the reaction mixture.
8. A process of Claim 1 wherein the alkali metal salt of iminodiacetic acid is the disodiurn salt.
9. A process for preparing N,N-diacetic acid aminomethylenephosphonic acid which comprises the steps of adding phosphorus trichloride to an aqueous solution of an alkali metal salt of iminadiacetic acid and forming a mixture of phosphorous acid and iminodiacetic acid hydrochloride and alkali metal chloride, 30 adding formaldehyde to said mixture to phosphonomethylate the iminodiacetic acid hydrochloride to produce N,N-diacetic acid aminomethyiene-phosphonic acid while simultaneously adding thereto a second quantity of the alkali metal salt of iminodiacetic acid, adding an amount of water to the reaction mixture sufficient to dissolve the alkali metal salt, neutralizing the excess hydrochloric acid in the resulting mixture, and separating the N,N-diacetic acid aminomethylenephosphonic acid.
10. The process of Claim 9 wherein the alkali metal salt of iminodiacetic acid is the disodium salt.
11. The process of Claim 9 wherein the alkali metal salt of iminodiacetic acid is the dipotassium salt.
12. Ina process for preparing N,N-diacetic acid aminomethylenephosphonic acid wherein iminodiaceto nitrile is hydrolyzed with an alkali metal base to provide the dialkali metal salt which is then converted to 40 iminodiacetic acid and then reacted in aqueous strong mineral acid solution with phosphorous acid and formaldehyde, the improvement which comprises reacting in series, the hydrolysate of iminodiacetonitrile containing an alkali metal salt of iminodiacetic acid in aqueous strong mineral acid solution to form the strong mineral acid salt of iminodiacetiG acid and an alkali metal salt; then phosphonomethylating by reacting the strong mineral acid salt with formaldehyde and phosphorous acid to provide N,N-diacetic acid 45 aminomethylenephosphonic acid and the alkali metal salt; adding an amount of waterto the reaction mixture sufficient to dissolvethe alkali metal salt and separating the N, N-diacetic acid aminomethylenephos phonic acid as a precipitate.
13. The process of Claim 12 wherein a portion of the alkali metal salt of iminodiacetiG acid is added during the phosphonomethylating step.
14. The process of Claim 12 wherein the strong mineral acid is hydrochloric acid.
15. The process of Claim 14 wherein the hydrogen chloride and phosphorous acid is provided by adding phosphorus trichloride to the aqueous reaction medium.
16. The process of Claim 14 wherein the water added subsequent to the phosphonomethylation step contains an amount of base sufficient to neutralize excess hydrogen chloride in the reaction mixture.
17. The process of Claim 14 wherein the alkali metal salt of iminodiacetic acid is the disodium salt.
18. The process of Claim 14 wherein the alkali metal salt of iminodiacetic acid is the dipotassium salt.
19. The process of Claim 17 wherein the phosphorus trichloride and the total amount of disodium salt of iminodiacetic acid are present in the reaction mixture in the mole ratio of about 0.8 to 1.4.
20. The process of Claim 1 wherein the strong mineral acid is sulfuric acid.
Printed in the UK for HMSO, D8818935, T85, 7102. Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
so
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58403884A | 1984-02-27 | 1984-02-27 | |
| US06/676,749 US4724103A (en) | 1984-02-27 | 1984-12-05 | Process for preparing N,N-diacetic acid aminomethylenephosphonic acid |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8504958D0 GB8504958D0 (en) | 1985-03-27 |
| GB2154589A true GB2154589A (en) | 1985-09-11 |
| GB2154589B GB2154589B (en) | 1987-04-08 |
Family
ID=27078970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08504958A Expired GB2154589B (en) | 1984-02-27 | 1985-02-26 | Improved process for preparing n,n-diacetic acid aminomethylenephosphonic acid |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4724103A (en) |
| EP (1) | EP0155926B1 (en) |
| KR (1) | KR870001766B1 (en) |
| AU (1) | AU568187B2 (en) |
| BR (1) | BR8500859A (en) |
| CA (1) | CA1240338A (en) |
| DE (1) | DE3564688D1 (en) |
| ES (3) | ES8606367A1 (en) |
| GB (1) | GB2154589B (en) |
| HU (1) | HUT39455A (en) |
| IL (1) | IL74454A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2215720A (en) * | 1988-02-08 | 1989-09-27 | Nitrokemia Ipartelepek | N-phosphono-methyl-imino-diacetic acid |
| WO1994015939A1 (en) * | 1993-01-14 | 1994-07-21 | Zeneca Limited | Process for the manufacture of n-phosphonomethyliminodiacetic acid |
| WO2010136574A1 (en) | 2009-05-28 | 2010-12-02 | Straitmark Holding Ag | Method for the manufacture of phosphonoalkyl iminodiacetic acids |
| WO2011051309A1 (en) | 2009-10-27 | 2011-05-05 | Straitmark Holding Ag | Method for the manufacture of phosphonoalkyl iminodiacetic acid |
| WO2014012986A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of n-phosphonomethyliminodiacetic acid |
| US9676799B2 (en) | 2012-07-17 | 2017-06-13 | Straitmark Holding Ag | Method for the synthesis of N-(phosphonomethyl)glycine |
| US10280189B2 (en) | 2012-07-17 | 2019-05-07 | Monsanto Technology Llc | Method for the synthesis of aminoalkylenephosphonic acid |
| US10464958B2 (en) | 2012-07-17 | 2019-11-05 | Monsanto Technology Llc | Method for the synthesis of alpha-aminoalkylenephosphonic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU205944B (en) * | 1988-02-08 | 1992-07-28 | Nitrokemia Ipartelepek | Process for producing n-phosphono-methyl-imino-diacetic acid |
| US5167866A (en) * | 1989-12-15 | 1992-12-01 | W. R. Grace & Co. Conn. | Control of corrosion in aqueous systems using certain phosphonomethyl amine oxides |
| US5312972A (en) * | 1992-10-29 | 1994-05-17 | Hampshire Chemical Corp. | Conversion of hydroxymethyl-iminodiacetic acid to phosphonomethyl-iminodiacetic acid |
| US5312973A (en) * | 1993-03-25 | 1994-05-17 | Finchimica S.P.A. | Process for producing n-phosphono-methyl-imino-diacetic acid |
| BR9607214A (en) * | 1995-03-14 | 1998-07-07 | Monsanto Co | Treatment of a stream of debris containing formaldehyde |
| US6365772B1 (en) | 1995-05-30 | 2002-04-02 | Hampshire Chemical Corp. | Facile synthesis of phosphonomethylglycine from phosphonomethyliminodiacetic acid |
| DK0833831T3 (en) * | 1995-06-07 | 2002-03-18 | Monsanto Technology Llc | Process for the preparation of N-phosphonomethyliminodiacetic acid |
| US5986128A (en) * | 1996-11-01 | 1999-11-16 | Monsanto Company | Use of monosodium iminodiacetic acid solutions in the preparation of N-phosphonomethyliminodiacetic acid |
| IES980552A2 (en) * | 1998-07-09 | 1999-08-11 | Agritech Chemical Ltd | Improved process for preparing N-phosphonomethyl iminodiacetic acid |
| BR9907000A (en) * | 1998-09-08 | 2000-09-26 | Hampshire Chemical Corp | Synthesis of phosphonomethyliminodiacetic acid with reduced effluent |
| AR029508A1 (en) * | 2000-04-14 | 2003-07-02 | Dow Agrosciences Llc | PROCESS TO REMOVE AND RECOVER SODIUM CHLORIDE FROM THE EFFLUENTS OF WASTE FROM THE MANUFACTURING PROCESSES OF THE N-PHOSPHOMETILIMINODIACETIC ACID (PMIDA) |
| US7015351B2 (en) * | 2000-05-22 | 2006-03-21 | Monsanto Technology Llc | Reaction systems for making N-(phosphonomethyl) glycine compounds |
| WO2002055527A1 (en) * | 2001-01-12 | 2002-07-18 | Basf Aktiengesellschaft | Method for producing n-phosphonomethyl iminodiacetic acid |
| US6641741B2 (en) | 2001-04-13 | 2003-11-04 | Dow Agrosciences Llc | Removal and recovery of chloride from phosphonomethyliminodiacetic acid process brine |
| AU2006241162A1 (en) * | 2005-04-25 | 2006-11-02 | Monsanto Technology Llc | Altering the crystal size distribution of N-(phosphonomethyl) iminodiacetic acid for improved filtration and product quality |
| CN100436460C (en) * | 2005-10-08 | 2008-11-26 | 重庆三峡英力化工有限公司 | Synthetic method for N-phosphonyl methyl imino diacetic acid |
| CN100400543C (en) * | 2006-09-08 | 2008-07-09 | 四川贝尔实业有限责任公司 | Method for preparing Phosphonomethyl iminodiacetic acid (PMIDA) through hydrolysis of imino diacetonitrile |
| CN101525350B (en) * | 2009-04-22 | 2012-07-18 | 北京颖新泰康国际贸易有限公司 | Method for preparing N-(phosphonomethyl)iminodiacetic acid |
| WO2012009860A1 (en) * | 2010-07-23 | 2012-01-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phosphonomethyl iminodiacetic acid |
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|---|---|---|---|---|
| US2609390A (en) * | 1950-06-01 | 1952-09-02 | Frederick C Bersworth | Phosphonic alkylene polyamino acids and method of producing same |
| US2895989A (en) * | 1956-06-22 | 1959-07-21 | Dow Chemical Co | Method for the preparation of iminodiacetic acid |
| NL285361A (en) * | 1961-11-13 | 1900-01-01 | ||
| GB1142294A (en) * | 1966-02-08 | 1969-02-05 | Albright & Wilson Mfg Ltd | Improvements in production of amino alkylene phosphonic acids |
| DE2021148A1 (en) * | 1970-04-30 | 1971-11-11 | Benckiser Gmbh Joh A | Process and plant for the continuous production of aminoalkylenephosphonic acids |
| US3904668A (en) * | 1973-11-15 | 1975-09-09 | Grace W R & Co | Process for preparing iminodiacetonitrile and alkali metal iminodiacetates |
| SE7703448L (en) * | 1976-03-29 | 1977-09-30 | Grace W R & Co | PROCEDURE FOR THE EXTRACTION OF GLYCIN AND IMINODIATIC ACID FROM SOLUTIONS CONTAINING SODIUM GLYCINATE AND DINATRIUMIMINODIACETATE |
| CH647528A5 (en) * | 1978-10-27 | 1985-01-31 | Bcap Biolog Chem Act Pat | PROCESS FOR THE PREPARATION OF N-phosphonomethylglycine. |
| US4389349A (en) * | 1982-01-25 | 1983-06-21 | Cho Hung H | Process for preparing of N-phosphenomethyl glycine |
| US4657705A (en) * | 1985-09-23 | 1987-04-14 | Monsanto Company | Process for the preparation of N-substituted aminomethylphosphonic acids |
-
1984
- 1984-12-05 US US06/676,749 patent/US4724103A/en not_active Expired - Lifetime
-
1985
- 1985-02-25 ES ES540675A patent/ES8606367A1/en not_active Expired
- 1985-02-26 DE DE8585870031T patent/DE3564688D1/en not_active Expired
- 1985-02-26 HU HU85711A patent/HUT39455A/en unknown
- 1985-02-26 CA CA000475168A patent/CA1240338A/en not_active Expired
- 1985-02-26 GB GB08504958A patent/GB2154589B/en not_active Expired
- 1985-02-26 KR KR1019850001194A patent/KR870001766B1/en not_active IP Right Cessation
- 1985-02-26 EP EP85870031A patent/EP0155926B1/en not_active Expired
- 1985-02-26 AU AU39138/85A patent/AU568187B2/en not_active Expired
- 1985-02-27 BR BR8500859A patent/BR8500859A/en not_active IP Right Cessation
- 1985-02-27 IL IL74454A patent/IL74454A/en not_active IP Right Cessation
-
1986
- 1986-01-09 ES ES550748A patent/ES8703887A1/en not_active Expired
- 1986-01-09 ES ES550749A patent/ES8703888A1/en not_active Expired
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2215720A (en) * | 1988-02-08 | 1989-09-27 | Nitrokemia Ipartelepek | N-phosphono-methyl-imino-diacetic acid |
| US4931585A (en) * | 1988-02-08 | 1990-06-05 | Nitrokemia Ipartelepek | Process for preparing N-phosphono-methyl-imino-diacetic acid |
| AU607040B2 (en) * | 1988-02-08 | 1991-02-21 | Nitrokemia Ipartelepek | Process for preparing n-phosphono-methyl-imino-diacetic acid |
| GB2215720B (en) * | 1988-02-08 | 1991-07-10 | Nitrokemia Ipartelepek | Process for preparing n-phosphono-methyl-imino-diacetic acid |
| AU675490B2 (en) * | 1993-01-14 | 1997-02-06 | Zeneca Limited | Process for the manufacture of N-phosphonomethyliminodiacetic acid |
| US5527953A (en) * | 1993-01-14 | 1996-06-18 | Zeneca Limited | Process for the manufacture of N-phosphonomethyliminodiacetic acid |
| WO1994015939A1 (en) * | 1993-01-14 | 1994-07-21 | Zeneca Limited | Process for the manufacture of n-phosphonomethyliminodiacetic acid |
| WO2010136574A1 (en) | 2009-05-28 | 2010-12-02 | Straitmark Holding Ag | Method for the manufacture of phosphonoalkyl iminodiacetic acids |
| WO2011051309A1 (en) | 2009-10-27 | 2011-05-05 | Straitmark Holding Ag | Method for the manufacture of phosphonoalkyl iminodiacetic acid |
| US9315528B2 (en) | 2009-10-27 | 2016-04-19 | Straitmark Holding Ag | Method for the manufacture of phosphonoalkyl iminodiacetic acid |
| WO2014012986A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of n-phosphonomethyliminodiacetic acid |
| US9676799B2 (en) | 2012-07-17 | 2017-06-13 | Straitmark Holding Ag | Method for the synthesis of N-(phosphonomethyl)glycine |
| US10280189B2 (en) | 2012-07-17 | 2019-05-07 | Monsanto Technology Llc | Method for the synthesis of aminoalkylenephosphonic acid |
| US10364262B2 (en) | 2012-07-17 | 2019-07-30 | Monsanto Technology Llc | Method for the synthesis of N-phosphonomethyliminodiacetic acid |
| US10464958B2 (en) | 2012-07-17 | 2019-11-05 | Monsanto Technology Llc | Method for the synthesis of alpha-aminoalkylenephosphonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3913885A (en) | 1985-09-05 |
| HUT39455A (en) | 1986-09-29 |
| US4724103A (en) | 1988-02-09 |
| GB8504958D0 (en) | 1985-03-27 |
| EP0155926B1 (en) | 1988-08-31 |
| KR850007062A (en) | 1985-10-30 |
| ES8703888A1 (en) | 1987-03-01 |
| KR870001766B1 (en) | 1987-10-06 |
| BR8500859A (en) | 1985-10-15 |
| CA1240338A (en) | 1988-08-09 |
| AU568187B2 (en) | 1987-12-17 |
| DE3564688D1 (en) | 1988-10-06 |
| IL74454A (en) | 1988-05-31 |
| ES550749A0 (en) | 1987-03-01 |
| ES8703887A1 (en) | 1987-03-01 |
| ES540675A0 (en) | 1986-04-16 |
| GB2154589B (en) | 1987-04-08 |
| ES8606367A1 (en) | 1986-04-16 |
| ES550748A0 (en) | 1987-03-01 |
| EP0155926A1 (en) | 1985-09-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 20050225 |